Chia-Yun Lai

Time dependent wettability of graphite upon ambient exposure: The role of water adsorption

We report the temporal evolution of the wettability of highly ordered pyrolytic graphite (HOPG) exposed to environmental conditions. Macroscopic wettability is investigated by static and dynamic contact angles (SCA and DCA) obtaining values comparable to the ones presented in the literature. SCA increases from ∼68° to ∼90° during the first hour of exposure after cleaving, whereas DCA is characterized by longer-scale (24 h) time evolution. We interpret these results in light of Fourier transform infrared spectroscopy, which indicates that the evolution of the HOPG wettability is due to adsorption of molecules from the surrounding atmosphere. This hypothesis is further confirmed by nanoscopic observations obtained by atomic force microscope (AFM)-based force spectroscopy, which monitor the evolution of surface properties with a spatial resolution superior to macroscopic experiments. Moreover, we observe that the results of macro- and nanoscale measurements evolve in similar fashion with time and we propose a quantitative correlation between SCA and AFM measurements. Our results suggest that the cause of the transition in the wettability of HOPG is due to the adsorption of hydrocarbon contaminations and water molecules from the environment. This is corroborated by annealing the HOPG is vacuum conditions at 150°, allowing the desorption of molecules on the surface, and thus re-establishing the initial macro and nano surface properties. Our findings can be used in the interpretation of the wettability of more complicated systems derived from HOPG (i.e., graphene).

Surface and Bulk Effects in Photochemical Reactions and Photomechanical Effects in Dynamic Molecular Crystals.

The increasing number of reports on photomechanical effects in molecular crystals necessitates systematic studies to understand the intrinsic and external effectors that determine and have predictive power of their type and magnitude. Differential light absorption and product gradient between the surface and the bulk of the crystal are often invoked to qualitatively explain the mechanical response of crystals to light; however, the details on how this difference in photochemical response accounts for macroscopic effects such as surface modification, deformation, or disintegration of crystals are yet to be established. Using both bulk- and surface-sensitive analytical techniques, a rare instance of benzylidenefuranone crystals is studied here, and it is capable of several distinct types of photomechanical response including surface striation and delamination, photosalient effect (ballistic disintegration and motion), and photoinduced bending by dimerization. The results provide a holistic view on these effects and set the stage for the development of overarching theoretical models to describe the photomechanics in the ordered solid state.

Systematic Multidimensional Quantification of Nanoscale Systems From Bimodal Atomic Force Microscopy Data

Here we explore the raw parameter space in air in bimodal atomic force microscopy (AFM) in order to enhance resolution, provide multiparameter maps, and produce suitable transformations that lead to physically intuitive maps general enough to be recognized by the broader community, i.e., stiffness, Hamaker constant, and adhesion force. We further consider model free transforms to enhance the raw parameter space in the form of alternative and more intelligible contrast maps. We employ highly oriented pyrolytic graphite, calcite, polypropylene, and dsDNA on mica to demonstrate a systematic form of parameter expansion. The proposed methodology to enhance and interpret a larger parameter space introduces a methodology to tractable multidimensional AFM from raw bimodal AFM maps.

Elucidation of the wettability of graphene through a multi-length-scale investigation approach

Univocal conclusions around the wettability of graphene exposed to environmental conditions remain elusive despite the recent efforts of several research groups. The main discrepancy rests on the question of whether a graphene monolayer (GML) is transparent or not to water and more generally what the role is that the substrate plays in determining the degree of wetting of the GML. In this work, we investigate the water transparency of GML by means of a multi-length-scale approach. We complement traditional static contact angle measurements and environmental scanning electron microscopy experiments with atomic force microscopy based force spectroscopy to assess the role that intermolecular interactions play in determining the wetting of GML. To gain deeper insight into the wetting transparency issue, we perform experiments on inert metals, such as gold and platinum, covered or not covered by GML. The comparison of the results obtained for different systems (i.e. GML covered and uncovered inert metals), provides unambiguous evidence that supports the non-wetting transparency theory of GML. This work aims to assist the development of technologies based on graphene–water interaction, such as graphitic membranes for water separation processes.

Periodicity in bimodal atomic force microscopy

Periodicity is fundamental for quantification and the application of conservation principles of many important systems. Here, we discuss periodicity in the context of bimodal atomic force microscopy (AFM). The relationship between the excited frequencies is shown to affect and control both experimental observables and the main expressions quantified via these observables, i.e., virial and energy transfer expressions, which form the basis of the bimodal AFM theory. The presence of a fundamental frequency further simplifies the theory and leads to close form solutions. Predictions are verified via numerical integration of the equation of motion and experimentally on a mica surface.

Nanoscale Hydrophilicity Studies of Gulf Parrotfish (Scarus persicus) Scales

The Gulf parrotfish (Scarus persicus) offers inspiration for a strategy to combat marine biofouling, a problem of great economic and environmental interest to the maritime community, through its use of a continually maintained, multifunctional, water-based mucus layer to cover its scales. In this study, to better understand the scale-mucus interface, we investigate the nanoscale hydrophilicity of the fish scales by comparing reconstructed force distance profiles obtained using an amplitude-modulation atomic force microscopy (AM-AFM) technique. We note significant differences between three morphologically distinct regions of each scale, as well as between scales from four spatially distinct regions of the fish. This study reveals a previously unreported property of fish scales and proves the value of a new AFM technique to the field of biomaterials.

Reconstruction of height of sub-nanometer steps with bimodal atomic force microscopy.

Obtaining topographic images of surfaces presenting terraces with heights in the nanometer and sub-nanometer range has become routine since the advent of atomic force microscopy (AFM). There remain however several open questions regarding the validity of direct topographic measurements. Here we turn to recent advances in AFM to correct the height of nanometric terraces by exploiting the four observables of bimodal AFM operated in the non-invasive attractive regime. We first derive expressions based on the van der Waals theory and then image model terraces in air in standard bimodal AFM while simultaneously correcting and decoupling the sources of loss/gain of height.

The Mendeleev–Meyer force project

Here we present the Mendeleev-Meyer Force Project which aims at tabulating all materials and substances in a fashion similar to the periodic table. The goal is to group and tabulate substances using nanoscale force footprints rather than atomic number or electronic configuration as in the periodic table. The process is divided into: (1) acquiring nanoscale force data from materials, (2) parameterizing the raw data into standardized input features to generate a library, (3) feeding the standardized library into an algorithm to generate, enhance or exploit a model to identify a material or property. We propose producing databases mimicking the Materials Genome Initiative, the Medical Literature Analysis and Retrieval System Online (MEDLARS) or the PRoteomics IDEntifications database (PRIDE) and making these searchable online via search engines mimicking Pubmed or the PRIDE web interface. A prototype exploiting deep learning algorithms, i.e. multilayer neural networks, is presented.

Multi-wall carbon nanostructured paper: characterization and potential applications definition

In the present work, a free-standing paper-like sample made of a three-dimensional web of multiwall carbon nanotubes that exhibit cross-linking and wall sharing is characterized with respect to its electrical, electrochemical, surface and wetting properties. All these parameters are studied simultaneously to assess the potential of the sample for demanding applications with multiple material requirements. It is observed that many characteristics of the one-dimensional counterpart are retained by the three-dimensional web. In addition, the properties of this nanostructured material are compared against zero-, one- two- and three-dimensional carbon-based materials, while potential applications that require high electrical conductivity and energy storage capabilities and related properties, are discussed.

Divergent surface properties of multidimensional sp (2) carbon allotropes: the effect of aging phenomena.

Despite the current interest in the scientific community in exploiting divergent surface properties of graphitic carbon allotropes, conclusive differentiation remains elusive even when dealing with parameters as fundamental as adhesion. Here, we set out to provide conclusive experimental evidence on the time evolution of the surface properties of highly oriented pyrolytic graphite (HOPG), graphene monolayer (GML) and multiwalled carbon nanotubes (MWCNTs) as we expose these materials to airborne contaminants, by providing (1) statistically significant results based on large datasets consisting of thousands of force measurements, and (2) errors sufficiently self-consistent to treat the comparison between datasets in atomic force microscopy (AFM) measurements. We first consider HOPG as a model system and then employ our results to draw conclusions from the GML and MWCNT samples. We find that the surface properties of aged HOPG are indistinguishable from those of aged GML and MWCNT, while being distinct from those of cleaved HOPG. Herein, we provide a sufficient body of evidence to disregard any divergence in surface properties for multidimensional sp (2) carbon allotropes that undergo similar aging processes.